Alkanol-ether-imides of long-chain aliphatic dicarboxylic compounds



Patented Dec. 15, 1953 ALKANOL-ETHER-IMIDES F LONG-CHAIN ALIPHATICDICARBOXYLIC COMPOUNDS John Ross, Ramsey, and Arthur- Ira. Gebhart,

Union, N'. 1., assignors to Colgate-Palmolive- Peet Company, Jersey ofDelaware City, N. .L, a corporation No Drawing. Application September20; 1949,- Serial- No. 116,854

Claims. (CI. 260-32655).

The present invention relates to new compounds which have usefulsurface-active properties and which are also useful as intermediates inorganic syntheses, and more particularly to novel alkanol-etherderivatives of certain organic 5 Ihe surface-active alkanol-ether-imidesrealiphatic imides and to processes for preparing ferred to are novelcompounds and may be prethe same. pared for incorporation in non-soapdetergents The novel surface-active compounds of this as aforementioned,or for other purposes, by invention are alkanol-ether-i'mides ofcondensacondensing,- a suitable nitrogen base with a simple ticnproducts of long-chain olefini'c, preferably condensation product of a.long-chain olefin and mono olefinic, hydrocarbons with aliphaticdialiphatic dicarboXyl-iccompound, viz, an alicarboxylic compounds, viz,aliphatic di'carboxylicphatic dicarboxylic acid, ester, or an anhydrideacids, esters oranhydri'deshaving an alpha-betahavingv analpha-beta-enal group, followed by enal group. Compounds of thischaracter which treating the resulting product with a hydroxyhave beenfound to be of particular value are ether-halohydrin to form thecorresponding such as are formed by treating imides of con-'alkanol-ether-imide derivative. The compounds densation products, forexample products resultof the invention may also be prepared by reacingfrom the condensation of long-chain olefins tion' of the imide of thecondensation productwith maleic anhydride, with alkanol-ether. halowithalkene oxide, such as ethylene oxide, to first hydrins or suitablealkene oxide derivatives form the alkanol derivative, and then reactingthereof; The compounds may be. represented this; alka-nol derivativewith more alkene oxide graphically by the following general formula: tointroduce.- additional alkoxy groups to thus (1) form analkanol-ether-imide compound.

FCECO The sulphated or sulphonated organic mate I I I as male employed mthe novel compositions accord.- N ('GHR' CHR OH ing to the presentinvention may be prepared R-CHCO from organic materials which areapplicable for where X represents a carbon chain of about 8sulphonatifln (true sulp ona ion and/or sulto about 24 carbon atoms, andpreferably 12 to phation), especially 1311088 having abOllt 3 t0 a Dut18 carbons whichchain may be saturated, un- Zi'tand preferably about 12to: about 18) carbon saturated, substituted or unsubstituted; R is hy-'atoms to the molecule, including fatty oils, undrogen or a short-chainalkyl group of from 1- saturated fatty acids; mineral oils, mineral oilto about 3 carbon atoms; R is hydrogen or a: extractsmonoandfldiglycerides, partial esters short-chain alkyl group or hydroxysubstituted or ethers of glycols, polyglycols, and polyalco alkyl groupof about 1 to 3 carbon atoms; m isahols, aromatic and alkylated aromaticcomsmall integer from 1' to 3; and n is a small inpounds, alcohols andolefins, coal tar distillates, teger from 1 to 4-. and numerous otherorganic compounds and in accordance with the present invention itmixtures of compounds. Suchcompounds can has been found that theincorporation of a small be sulphonat'ed'. by any of several methods andproportion of surface-active alkanol-ether- 46 may form any of severalproducts, depending imides of condensation products of' long-chain uponthe method ofv sulphonation employed. reins with aliphatic dicarboxyli'ccompounds, The sulphonated. or sulphated organic comvm, aliphaticdicarboxylic acids, esters and anpounds include sulphonated mineral oilvor conhyd-rides having an alpha-beta-enal group with ventional mineraloil refinery sludges; sulphoa non-soap detergent, emulsifier and wettinghated mineral oil extracts; sulphonated fatty 2 sulphonated orsulphatedorganic materials provides a composition which in aqueous solutionpossesses greatly improved sudsing, deterging and foaming properties.

agent of the type of acids and oils, including sulphonated castor oil,sulphorricinoleic acid, sulphonated olive and sulpho-oleic acid,aliphatic sulphonates and sulphates, including cetyl sulphuric acid,dodecyl acid sulphate, and tetradecanehydroxy sulphonic acid-1,2;aliphatic ether and ester sulphonates including the dodecyl ether ofhydroxy ethyl sulphonic acid, the cetyl ether of glyceryl sulphonicacid, and coconut oil monoglyceride monosulphate; sulphonates preparedby treatment of organic materials with sulphur dioxide and chlorine inthe presence of light followed by hydrolysis of the product; sulphonatesprepared by treatment of organic bodies with sulphuryl chloride and anactivating agent in the presence of light followed by hydrolysis of theproduct: fatty acid; fatty acid amides of amino alkyl sulphonic acids,including lauric amide of taurine and tall oil acid amide of aminoglyceryl sulphonic acid; sulphonic acids of naphthenes and naphthenicacids; lignin sulphonic acids; aromatic and alkylated aromatic sulphonicacids, including naphthalene sulphonic acid, octadecyl benzene sulphonicacid, and dodecyl naphthalene sulphonic acid: the product of a mineraloil extract sulphonated while dissolved in liquid sulphur dioxide; andinnumerable other organic sulphonic and sulphuric acid derivatives ormixtures thereof. These organic sulphate and true sulphonate compoundsinclude those in which the organic radicals of the molecule areunsubstituted or those which contain substituents, such as halogens,hydroxyls, nitrogen-containing groups, acyl groups, acyloxy groups,alkoxy groups etc.

Of these sulphated and sulphonated materials,

the most suitable for inclusion in the novel compositions of the presentinvention are normally non-alkaline (having a pH below 7.0) andespecially those having carboxylic ester linkages, in-

cluding the sodium salts of the sulphuric acid esters of coconut oilfatty acid monoglycerides, tallow diglycerides monosulphate, etc.

The imides of the condensation products from which thealkanol-ether-imides are obtained include those having from about '12 toabout 28 and preferably about 16 to about 22 carbon atoms per molecule.The carbon chains or the imide molecule may be straight or branched,saturated or unsaturated, and they may be either unsubstituted orsubstituted by substituents such as halogens, hydroxyl, acyl groups,acvloxy groups, alkoxy groups, aryl groups, etc., although it isgenerally preferred that any substituent groups that are of ahydrophil-ic character be located near or adjacent to the imide group.alkanol-ether-imides emploved in the process of this invention may alsoinclude compounds having cyclic substituents containing in addition analiphatic side chain of about 8 to 24 carbon atoms, although suchcompounds are generally not a preferred type.

While the alkanol-ether-imide compounds, when used as organic buildersin non-soap synthetic detergents as referred to heretofore may be addedin amounts varying from about 0.01% to about 50% by weight based uponthe active ingredients of the detergent composition, it is preferred toincorporate from 0.1% to about 20%, and preferably about 1% to 10% byweight of the active ingredients. The optimum proportion employed willvary with the particular active ingredients used; with the proportion ofother ingredients present, if any, and to some degree with the strengthor concentration of the solution, to be formed in use.

The Y The organic builder may be incorporated with the other activeingredient or mixture to form the novel composition of this invention atany point during the manufacturing process at which subsequentoperations will not destroy or objectionably modify the builder or causea deleterious reaction between the builder and any other material in thecomposition. In general, it is preferred to add the builder at a pointin the manufacturing subsequent to the hydrolyzing and/or neutralizingstep. This may be accomplished by adding the organic builder tosolutions containing the other active ingredient or ingredients bymixing the builder with the solid active ingredient in comminuted form,or by adding the builder to a solution of the active ingredient andthereafter subjecting the solution containing active ingredient andorganic builder to spray-drying, roll-drying, etc., to form a solidcomposition.

Thus the novel compositions may be made up in solutions preferablyconcentrated, or a dry or partially hydrated solid product may beformed. The product may be made in a more or less finely dividedcondition, which permits its ready transformation into flakes or otherphysical forms, for example by passing between a pair of proper- 1yspaced rolls, or by pressing into cakes, or by other means, with orwithout addition of modifying agents.

Adjuvant materials may be admixed with the sulphonate salts by mixingthe adjuvant materials with the sulphonated organic compounds and/or theneutralizing agents before neutralization or flashing, by simultaneouslyflashing a second solution containing such adjuvant materials, and/or bymixing the final product therewith. When added after neutralization, theadjuvant materials may be added before, after, or simultaneously withthe organic builder. Such adjuvant material may include any of thesubstances employed by the art in admixture with sulphonated organicdetergents generally, care being exercised to avoid the use of anymaterial which would remove or otherwise substantially diminish theeffectiveness of the particular organic builder incorporated. The typeof addition agent will depend upon the intended ultimate use of the newcomposition.

In preparing the alkanol-ether-imide compounds of this invention thestarting material is a condensation product such as may be produced, forexample, by reacting maleic anhydride with a monoolefinic hydrocarbonfor example hexadecene, at temperatures of between 200 and 250C. Insteadof hexadecene there may be used non-conjugated poly-olefinic acids oresters. Examples of other olefinic compounds as well as other aliphaticdicarboxylic compounds, viz, aliphatic dicarboxylic acids, esters, andanhydrides having analpha-beta-enal group which are suitable for use inthis invention may be found in the copending patent application, SerialNumber 693,571, filed August 28, 1946, by John Ross et al., now U. S.Patent 2,496,353, issued on February '7, 1950, to which furtherreference may be made. The dicarboxylic anhydride olefinic condensationproduct or a mixture of condensation products as thus formed is thentreated with ammonia to form the imide derivative. If desired, thedouble bond or bonds of the dicarboxylic olefinic condensation productor mixture of condensation products may be suitably hydrogenated orhydroxylated to form the saturated derivatives, or saturated substitutedderivatives thereof, which in turn are reacted with ammonia 2 662,,89S 5to form the corresponding imide of the condensa- Upon reacting: theimlde, or preferably the salt 2 n g The i of g gi thereof, such as thepetssmm salt of the i'mide pro no usformetf en'isreac e wit- -e apapropriate hydroxy-ether haloh-ydri'n; such as g g f i example f i f f fichler fl. hydroxy ethyr ether, ,yiembrfluhyb 5 die yl et e1 e corresponmg ethano imide ehoxy-propyl ether, or similar bromhydni'rr com compound1s formed s w GHSQ IZMB CH: OH- C H:

HCO

NK QLGHPCHr-O-CHTCHzOH omoo 7 OHaCCHzIizCH=OH-CH2 onco N-QnHO-C1H4QHor-noo KCl pounds, or alkene' oxide derivatives to form the When theethanol-ether imide derivatives are desired alkanoI-ether-imidecompounds. 2 prepared using a short-chain aliphatic compound modifiedmethod; which also may be ernpl o i containing an epoxy oxygen atom asreactants, 22 g? i gi g g g gbg ifigg gi an excess of the alkene oxideis employedxto form a halohydrin, such as ethylene chlorhydrin to thepolyethylene 8th?! .den.vat1ves or ubst1tuted farm the, canespondingalkanehmide derivative 25 polyethylene ether derivatlves according tothe and their reacting this resultant alkaimlimide I'OHOWl-ng equations,wherein m is a Small integer with ug oxide mi m t alkaneleetherof from 1to 3. Starting with A-4,5-octadeceneimide compound; Imides' of the:various longi- ',2-dicarboxy1 f acid i id'e for example!CH:;("GH2')'12CH'=CH-f-)H:

cHco

h f 3 "q; j q" sy fagents 55 the alkali metal salt or the imide is firsttreated g ig ggfgf 1S adfiacen tonne of with halohydrin to form thecorresponding al- The olefinic dicarboxyl-ic compound condensakanolamine derivative, and then this resultant tion produet isconvertedinto the correspondin alkanol product is reacted with alkene oxide toimide by reacting the same under substantially 60 form the.alkanol-ether-imide. compound. The a hydr o rl iti w h d y a mon asalkali: metal salt or the: d-icarboxy-lic imide coni ag f g% :3:densation: product; maylbet converted to the" salt, fifgfigg ggfifg mz zgg g im for example the" potasiumsalt; by dissolving the lows, startingwith. n-fii-ootadecenelfl-diear- 5 imi'd'e condenstio'n product in ethylalcohol and boxylic acid anhydride fon-example: adding? alcoholic KO-H.The two-step method oHi('ctEn)w0H=oH-om.

7. starting with the potassium salt may be graphically illustrated asfollows:

The alkanol-ether-imides as prepared according to this invention possessuniquely desirable properties as organic builders, and are particularlyvaluable as foaming stabilizers. Further, the novel compounds andcompositions formed therefrom as herein disclosed exhibit surface-activeproperties in both acid and alkaline media, apparently changing from asubstantially neutral character to a non-ionized or an ionic form.

The compounds and compositions provided may be made up in solutions,either concentrated or diluted, or as dehydrated or as partially solidproduct. mixed with the new compounds or compositions made therefrom toform flakes, granular particles, cakes or other desired physical forms.Such adjuvant materials as sodium chloride, so-

Adjuvant materials may be also adk dium sulfate, sodium pyrophosphateand the like builders and fillers as may be employed in the soap andsynthetic detergent art may be utilized for this purpose. The particulartype of addition agent used in any case will depend on the ultimate useand character of the product desired.

The following examples are given to illustrate how the present inventionis utilized but it is to be understood that the invention is not limitedthereto. The parts specified are by weight.

Example I roxide to combine with the hydrochloric acid produced. Theresulting condensation product is principally fi-hydroxy-ethyl ether ofA4,5-octa-' decene-1,2 dicarboxylic acid ethanolimidewhich forms a waxysolid and is characterized by, its excellent surface-active propertiesand valuable utility as an organic builder.

8 Example II -A quantity of A4,5-tetradecene 1,2 dicarboxylic acidanhydride is heated above its melting point and dry ammonia gas isbubbled into the molten mass until no more ammonia is absorbed. Thistakes approximately one hour, during which time the temperature isgradually raised. The reaction mass is thereafter allowed to cool andthe solid reaction product comprising the resultant dicarboxylic acidimide is then heated to form a melt and reacted withB-chlor-;3-hydroxyethyl ether, the reactants being used in approximatelyequal molecular proportions, and with sufiicient sodium hydroxide beingadded to combine with the hydrochloric acid formed during the reaction.The resulting product consists mostly of the e-hydroxy-ethyl-etherderivative of A45 tetradecene-l-dicarboxylic acid imide, which productis soluble in water and is characterized by its surface-activeproperties and good builder characteristics.

Example III A quantity of A4,5-octadecene 1,2 dicarboxylic acidanhydride is heated to 150 C. and dry ammonia reacted therewith to formthe imide derivative, as described in Example I. The resultant imidecondensation product is then dissolved in ethyl alcohol and converted tothe potassium salt by the addition of alcoholic KOH. The potassium saltof the imide is thereafter reacted with ethylene chlorohydrin to formthe ethanolimide derivative. After removal of 3201 the resultantethanolimide derivative is treated with ethylene oxide to form thecorresponding ethanol-ether derivative of A4,5-octadecene 1,2 carboxylicacid imide condensation product.

The alkanol-ether-imide derivatives prepared as described may be usedalone as desired or may be sulphated and thus utilized, or admixed withsulphated or sulphonated non-soap substances to enhance theiremulsifying and detergent properties as described. When employing thenovel compounds of the present invention as organic builders, additionsof from 0.01% to about 59% of the weight of the active ingredients inthe surface-active composition may be made, but it is preferred toincorporate about 1% to 20% of organic builder based upon the weight ofactive ingredients.

In order to illustrate more clearly how the novel compounds of theinvention may be utilized as organic builders in detergent compositionsthere is set forth the following examples:

Example A To a synthetic detergent composition compriw ing about 40parts by weight of sodium salt of sulphuric acid ester of monoglycerides(of coconut oil fatty acids) and about 60 parts of sodium sulphate isadded 10 parts of s-hydroxy-ethyl ether of A4,5-octadecene-1,2dicarboxylic acid ethanolimide. Sufficient water is added to form asolution of the mixture and the solution is then spray dried to producea solid detergent compo sition having improved detergencycharacteristics.

Example B Twenty-five parts of B-hydroxy-ethyl-ether derivative of A4,5tetradecene-l-dicarboxylic acid imide (Example II) is added to parts ofso dium lauryl sulphate to form a synthetic detergent composition whichexhibits good foaming and sudsin characteristics.

Example 0 The alkanol-ether-imide condensation product consistingprincipally of B-hydroxy-ethyl-ether of 4,5-octadecene-1,2 dicarboxylicacid ethanolimide is heated to form a melt and spray cooled to transformit into discrete particles. The molten alkanol-ether-imide is spraycooled to form pellets by suitably forcing the melted material through aspray nozzle arranged in a spray chamher, and in which a current ofcooling air is kept moving to cool and solidify the dispersed dropletsof the alkanol-ether-imide as discharged from the spray nozzle.

The use of the term sulphonated with reference to organic compounds inthe following claims will be understood to include sulphated as well astrue sulphonated materials.

While various specific examples of preferred compositions and methodsembodying the present invention have been described, it will be apparentto those skilled in the art that many changes and modifications may bemade in the methods of procedure and that a wide variety of specificreagents may be employed to carry out the procedure. It is accordinglyto be understood that the examples given and the particular proportionsand details of the method procedure as set forth are intended to beillustrative only, and are not limitative of the scope of the invention,except as defined by the appended claims.

What is claimed is:

1. A new chemical compound of the following formula:

X-CHOO where X represents a carbon chain of about 8 to 24 carbon atoms,R is a material selected from the group consisting of hydrogen andshort-chain alkyl groups of from 1 to 3 carbon atoms, R is a materialselected from the group consisting of hydrogen and short-chain alkylgroups and hydroxy substituted alkyl group of about 1 to 3 carbon atoms,m is a. small integer from 1 to 3 and n is a small integer from 1 to 4.

2. As a new composition of matter, a chemical compound as described inclaim 1 which is in the form of discrete particles.

3. A process for preparing long-chain alkanoletherimide compounds whichcomprises condensing a long-chain olefin with an aliphatic 1,2dicarboxylic compound having an alpha-beta-enal group, said dicarboxyliccompound having a substituent selected from the group consisting ofhydrogen and an alkyl group having 1 to 3 carbon atoms, reacting theresultant condensation product with ammonia to produce an imide of saidcondensation product, converting said imide condensation product to asalt selected from the group consisting of the sodium and potassiumsalts of the said imide condensation product, reacting the salt of saidimide condensation product with an alkyl halohydrin to produce analkanolimide derivative, and reacting the resultant alkanolimidecompound with an alkene oxide to form the alkanol-ether-imidederivative.

4. A process for preparing an alkanol-etherimide which comprisescondensing an olefinic hydrocarbon compound having 8 to 24 carbon atomsper molecule with an aliphatic 1,2 dicarboxylic compound having analpha-beta-enal group, said dicarboxylic compound having a substituentselected from the group consisting of hydrogen and an alkyl group having1 to 3 carbon atoms, reacting the resultant condensation product withammonia to produce an imide of said condensation product, and thereafterreacting the imide of said condensation product with anhydroxy-etherhalohydrin to produce the alkanol-ether-imide.

5. A process for preparing an alkanol-etherimide which comprisescondensing an olefinic hydrocarbon compound having 8 to 24 carbon atomsper molecule 'with an aliphatic 1,2 dicarboxylic compound having analpha-beta-enal group, said dicarboxylic compound having a substituentselected from the group consisting of hydrogen and an alkyl group having1 to 3 carbon atoms, reacting the resultant condensation product witham? monia to produce an imide of said condensation product, reacting theimide of said condensation product with a compound selected from thegroup consisting of alkyl halohydrins and alkene oxide derivatives ofalkyl halohydrins to produce an alkanol-imide derivative thereof, andreacting the resultant alkanol-imide derivative with an alkene oxide toform the alkanol-ether-imide.

JOHN ROSS. ARTHUR IRA GEBHART.

References Cited in the file of this patent UNITED STATES PATENTS RossFeb. 7, 1950

1. A NEW CHEMICAL COMPOUND OF THE FOLLOWING FORMULA: